JPH0848508A - Cyclohexa phosphate and its production - Google Patents

Abstract

PURPOSE:To produce cyclohexaguanidine phosphate dehydrate by allowing cyclohexalithium phosphate to react with guanidine carbonate or guanidine phosphate in an aq. soln. CONSTITUTION:The cyclohexaguanidine phosphate dehydrate is produced by the following method. 85wt.% orthophosphoric acid is mixed with lithium carbonate in a mol. ratio of 10:7 in a porcelain dish and heated with an electric furnace for 1hr at 200 deg.C, for 5hr at 275 deg.C and for 3hr at 420 deg.C at last. The product is ground and mixed with an EDTA soln. adjusted to pH 9 with lithium hydroxide and the soln. is stirred for 2hr. The mixture is filtered and methanol is added to the filtered liq. Then, the mixed liq. is filtered, and lithium chloride is added to this filtered liq. to obtain a white precipitate. This precipitate is made to 10wt.% aq. soln. and passed through a cation exchange resin to remove lithium ion. The white precipitate is obtained by adding the guanidine carbonate or the guanidine phosphate under cooling the soln. with ice and after leaving to stand in a refrigerator for a day. This precipitate is washed with 80vol.% acetone aq. soln. to obtain the object product expressed by the formula.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclohexaphosphate, guanidine cyclohexaphosphate dihydrate, ammonium cyclohexaphosphate monohydrate and a method for producing them. Phosphate has long been used as a raw material for chemical fertilizers, and in recent years condensed phosphates have become widely used as water treatment agents, food additives, flame retardants, various ceramic materials, biomaterials, and electronic materials. , Its application has a great spread. The guanidine cyclohexaphosphate dihydrate and the ammonium cyclohexaphosphate monohydrate of the present invention are useful as novel phosphates in the above-mentioned fields.

[0002]

2. Description of the Related Art Conventionally, condensed phosphates have been extensively studied, for example, heteroatom chemistry (He).
teroat. Chem. ) 1991, Volume 2, Issue 5,
On pages 587-592, we report the synthesis of cyclooctaphosphate sodium salt and its thermal properties. However, a method for synthesizing guanidine cyclohexaphosphate and ammonium cyclohexaphosphate, which are cyclohexaphosphate, has not been established.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that a novel condensed phosphate, guanidine cyclohexaphosphate, which is useful as a water treatment agent, food additive, flame retardant, various ceramic materials, biomaterials and electronic materials, and An intensive study was conducted to obtain ammonium cyclohexaphosphate. As a result, by dissolving lithium cyclohexaphosphate hexahydrate in water and substituting it with a guanidine group or an ammonium ion through a cation exchange resin, a novel condensed phosphate, guanidine dicyclohexaphosphate, is obtained. It was found that a hydrate or ammonium cyclohexaphosphate monohydrate was obtained, and based on this finding, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a novel condensed phosphate, guanidine cyclohexaphosphate dihydrate, ammonium cyclohexaphosphate monohydrate, and a method for producing them. Is.

[0004]

The present invention has the following configuration. (1) Guanidine cyclohexaphosphate dihydrate having the structure of the following chemical formula 3.

[Chemical 3] (2) Ammonium cyclohexaphosphate monohydrate having the structure of Chemical formula 4 below.

[Chemical 4] (3) A method for producing guanidine cyclohexaphosphate dihydrate, which comprises reacting lithium cyclohexaphosphate hexahydrate with guanidine carbonate or guanidine phosphate in an aqueous solution. (4) A method for producing ammonium cyclohexaphosphate monohydrate, which comprises reacting lithium cyclohexaphosphate with an aqueous ammonium solution in an aqueous solution.

The lithium cyclohexaphosphate hexahydrate used in the present invention can be obtained as follows. That is,
85% by weight of orthophosphoric acid and lithium carbonate in a molar ratio of 1
Mix in a magnetic dish at 0: 7 and heat in an electric furnace at 200 ° C. for 1 hour, 275 ° C. for 5 hours, and finally 420 ° C. for 3 hours. The obtained product is pulverized and PH9 is added with lithium hydroxide.
Prepared ethylenediamine tetraacetate (EDT
A) Mix with solution and stir for 2 hours. A slight precipitate occurs upon mixing the EDTA solution, so the solution is filtered to remove insoluble material. While cooling with ice, methanol is added to the obtained filtrate and the mixture is stirred.
Then, the solution is filtered again with a filter to remove insoluble substances, and lithium chloride is added to the obtained filtrate to obtain a white precipitate. It can be obtained by thoroughly washing the obtained white precipitate with a 75% by volume aqueous acetone solution (acetone 75: water 25), and then naturally drying.

The guanidine cyclohexaphosphate dihydrate and the ammonium cyclohexaphosphate monohydrate of the present invention can be obtained by the following method. That is, the lithium ion is removed by passing a 10 wt% aqueous solution of lithium cyclohexaphosphate hexahydrate obtained by the above method through a cation exchange resin. Then, the sample solution was ice-cooled, guanidine phosphate or guanidine carbonate or an aqueous ammonia solution was added with stirring, and the mixture was allowed to stand overnight in the refrigerator to obtain a white precipitate.
It is obtained by washing with a 0% by volume aqueous acetone solution (acetone 80: water 20) and air-drying.

[0007]

EXAMPLES In order to specifically describe the present invention, examples will be shown below. The product was analyzed by the method shown below. (1) X-ray Diffraction Method The sample was crushed in an agate mortar, mounted on a glass holder, and measured by a RAD-1B type X-ray diffractometer manufactured by Rigaku Denki Co. (2) Total Phosphorus Concentration Measurement The measurement was carried out in accordance with the official analytical method for fertilizer, the vanadomolybdate ammonium method. That is, 2 g of sample is 30 ml with 40 ml of aqua regia.
After heating and decomposing for a minute, a fixed amount of the solution is put into a measuring flask, and 20 ml of a nitric acid aqueous solution in which ammonium metavanadate and ammonium molybdate, which are color developing solutions, are dissolved is added,
The absorbance at a wavelength of 420 nm is measured, and the total phosphorus concentration is calculated from a calibration curve obtained from an aqueous solution of monopotassium phosphate as a standard solution. (3) Total carbon concentration measurement measuring device CHN coder M manufactured by Yanako Analytical Industry Co., Ltd.
It was performed using T-5. (4) Measurement of Total Nitrogen Concentration The measurement was performed according to the sulfuric acid method, which is an official analytical method for fertilizers. That is, 1 g of the sample is placed in a 500 ml Kjeldahl flask, 20 ml of concentrated sulfuric acid, 1 g of copper sulfate and 9 g of potassium sulfate are added,
Perform pyrolysis for 2 hours. After cooling, sodium hydroxide is added to make the mixture alkaline and then steam distillation is performed. The effluent is collected in 35 ml of 0.5N sulfuric acid, and back titration is performed with a 0.5N aqueous sodium hydroxide solution to calculate the total nitrogen concentration. (5) Infrared spectroscopic analysis Measured with an infrared analyzer FTIR-8000 manufactured by Shimadzu Corporation. (6) Measurement of hydration amount Rigaku Denki's TAS100 has a heating rate of 5 ° C./mi
n, measured in a dry atmosphere.

The lithium cyclohexaphosphate hexahydrate used in the examples was obtained by the following method. 20.5 ml of 85 wt% concentration of orthophosphoric acid and 15.6 g of lithium carbonate are mixed in a magnetic dish. Since carbon dioxide gas is generated by the mixing, the carbon dioxide gas is sufficiently deaerated, and then heated in an electric furnace at 200 ° C. for 1 hour. This is cooled in a desiccator, crushed, and heated again in an electric furnace at 275 ° C. for 5 hours. Similarly, after cooling and pulverizing, the mixture is heated again at 420 ° C. for 3 hours, cooled and pulverized. The heated product thus obtained was adjusted to pH 9 with lithium hydroxide, and 100 m of a 1 wt% EDTA solution was prepared.
1 and stirred for 2 hours. Insoluble substances were removed with a G4 glass filter, and 110 ml of methanol was added to the filtrate while cooling with ice. After removing the precipitate generated by the addition of methanol, 18 g of lithium chloride is added.
A slight precipitate forms, which is removed and 18.5 g of lithium chloride are added again. If stirring is continued for a while, a white precipitate is formed. This precipitate is filtered off, washed thoroughly with a 75% by volume aqueous acetone solution, and then naturally dried in the atmosphere to obtain lithium cyclohexaphosphate hexahydrate. 5.5 g of hydrate was obtained.

Example 1 2 g of lithium cyclohexaphosphate hexahydrate was dissolved in 20 ml of pure water to prepare an aqueous solution, and this aqueous solution was passed through a cation exchange resin kept at about 3 ° C. to remove lithium ions. The sample solution passed through the cation exchange resin was collected in the range of PH2 or higher. While the sample solution was cooled with ice, 2 g of guanidine carbonate was added, and the mixture was allowed to stand in the refrigerator for a whole day and night to obtain a white precipitate. 80% by volume of this white precipitate
Was washed 5 times with an aqueous acetone solution of, and further washed 5 times with acetone. It was naturally dried in the air for 48 hours to obtain 2.5 g of guanidine cyclohexaphosphate dihydrate. The results of elemental analysis of the obtained product were C: 8.21% by weight, P: 21.
6% by weight and N: 28.2% by weight (theoretical value C: 8.34% by weight, P: 21.4% by weight, N: 29.0% by weight). An X-ray diffraction diagram is shown in FIG. 1, an infrared absorption spectrum diagram is shown in FIG. 4, and a thermal analysis result is shown in FIG. From the X-ray diffraction diagram of FIG. 1, the product obtained in Example 1 shows an X-ray diffraction pattern completely different from that of the starting material lithium cyclohexaphosphate, and from the infrared absorption spectrum diagram of FIG.
A strong peak based on a guanidine group can be confirmed at 70 cm ^-1 . Furthermore, from the thermal analysis of FIG. 6, it was possible to confirm the endotherm and weight loss due to the elimination of bimolecular water of crystallization. From the above, it was confirmed that the product obtained in Example 1 was guanidine cyclohexaphosphate dihydrate represented by Chemical formula 3.

Example 2 Lithium cyclohexaphosphate hexahydrate (2 g) was dissolved in pure water (20 ml) to prepare an aqueous solution, and the aqueous solution was passed through a cation exchange resin kept at about 3 ° C. to remove lithium ions. The sample solution passed through the cation exchange resin was collected in the range of PH2 or higher. 29% by weight while cooling the sample solution with ice
After adding 7 g of the aqueous ammonia solution in (1), the mixture was allowed to stand in the refrigerator for a whole day and night to obtain a white precipitate. 80% by volume of this white precipitate
Was washed 5 times with an aqueous acetone solution of, and further washed 5 times with acetone. The product was naturally dried for 48 hours in air.
6 g were obtained. The result of elemental analysis of the obtained product is P: 3
0.7% by weight, N: 14.6% by weight (theoretical value P: 31.
6% by weight, N: 14.3% by weight). An X-ray diffraction diagram is shown in FIG. 2, an infrared absorption spectrum diagram is shown in FIG. 5, and a thermal analysis result is shown in FIG. From the X-ray diffraction diagram shown in FIG. 2, the product obtained in Example 2 shows an X-ray diffraction pattern which is completely different from that of the starting material lithium cyclohexaphosphate, and from the infrared absorption spectrum diagram of FIG. 1400 cm ^-1
In addition, a strong peak due to ammonium ion (NH ₄ ⁺ ) could be confirmed, and further, from the thermal analysis of FIG. 7, it was possible to confirm the endotherm and weight loss due to the desorption of one molecule of crystal water. From the above, it was confirmed that the product of Example 2 was the ammonium hexamonophosphate monohydrate represented by Chemical formula 4.

[0011]

Industrial Applicability The guanidine cyclohexaphosphate dihydrate and the ammonium cyclohexaphosphate monohydrate of the present invention are used as water treatment agents, food additives, flame retardants, various ceramic materials, biomaterials and electronic materials. It is a useful novel condensed phosphate.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction pattern of the guanidine cyclohexaphosphate dihydrate obtained in Example 1, and FIG. 2 is an X-ray diffraction diagram of the ammonium cyclohexaphosphate monohydrate obtained in Example 2. Figure 3
Is an X-ray diffraction diagram of lithium cyclohexaphosphate as a raw material, FIG. 4 is an infrared absorption spectrum diagram of guanidine cyclohexaphosphate dihydrate, and FIG. 5 is an infrared absorption spectrum of ammonium cyclohexaphosphate monohydrate. Fig. 6 shows a thermal analysis chart of guanidine cyclohexaphosphate dihydrate, and Fig. 7 shows a thermal analysis chart of ammonium cyclohexaphosphate monohydrate.
Shown respectively.

Claims (4)

[Claims] 1. A guanidine cyclohexaphosphate dihydrate having a structure of the following chemical formula 1. Embedded image 2. An ammonium cyclohexaphosphate monohydrate having a structure of the following chemical formula 2. Embedded image 3. A process for producing guanidine cyclohexaphosphate dihydrate, which comprises reacting lithium cyclohexaphosphate hexahydrate with guanidine carbonate or guanidine phosphate in an aqueous solution. 4. A process for producing ammonium cyclohexaphosphate monohydrate, which comprises reacting lithium cyclohexaphosphate with an aqueous ammonium solution in an aqueous solution.